3-methylene-6-nitro-n-substituted isoindolones-(1)

ABSTRACT

3-METHYLENE-6-NITRO-N-substituted isoindolones-(1) produced by reacting 6-nitro-N-substituted isoindolones-(1) with formaldehyde or an agent yielding formaldehyde. The new compounds are starting materials for the production of dyes.

Elnited States Patent [191 Schefczik 3-ME'IHYLENE-6-NITRO-N-SUBSTITUIED ISOINDOLONES-( 1) [75] Inventor: Ernst Schefczik, Ludwigshafen,

Germany [73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, s hatfe lkhnfiermaay. [22] Filed: Nov. 8, 1971 21 Appl. No.: 196,787

[52] US. Cl. 260/325 [51] Int. Cl C07d 27/50 [58] Field of Search 260/325 [451 June 18, 1974 [5 6] References Cited UNITED STATES PATENTS 3,224,999 12/1965 Walker 260/415 Primary Examiner-Joseph A. Narcavage Attorney, Agent, or FirmJohnston, Keil, Thompson & Shurtleff 1 Claim, No Drawings 3-METHYLENE-6-NlTRO-N-SUBS I i ISOINDOLONES-( l The invention relates to compounds of the general n is one of the integers 1 and b 2;

R is unsubstituted or substituted alkyl or cycloalkyl when n is 1, or 1 alkylene of two to six carbon atoms or cyclohexylene when n is 2,

and also to a process for the production of these compounds.

R may, for example, be alkyl of one to eight carbon atoms, hydroxyalkyl of two to six carbon atoms, alkoxyalkyl of a total of three to eight carbon atoms or cycloalkyl of live to eight ring members, and also ethylene, propylene, butylene, hexylene or cyclohexylene- In particular, when n denotes 1, the following are suitable: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, B-ethylhexyl, B-hydroxyethyl, B-hydroxypropyl, 'y-hydroxypropyl, B-methoxyethyl, y-methoxypropyl, y-ethoxypropyl, 'y-butoxypropyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, cyclooctyl and radicals of the formulae: -C H CONH C H.,COOH, C l-l COOCl-l C H,COOC H C l-l CON(C1-l,-,) C l-l CON(C l-l C2H4C0NHC4H9, Or C l-l CON(CH CH- OH) Alkyl and alkoxyalkyl are preferred for R.

The process for the production of compounds of the formula (1) consists in reacting a compound of the form afl la OzN with formaldehyde or with an agent yielding formalde- 6 hyde.

The process is expediently carried out by reacting the nitro compound in aqueous or aqueous-organic formaldehyde solution, preferably in the presence of a basic condensing agent.

Examples of basic condensing agents are: piperidine,

BiF llfi99529919912319??? i lylaeine sigh;

2 .ylamine, potassium carbonate, sodium carbonate, so-

dium hydroxide and potassium hydroxide.

Examples of agents yielding formaldehyde are paraformaldehyde and urotropine, but the use of formaldehyde itself is preferred.

The reaction is preferably carried out at elevated temperature, for example 79 to C. It is sufficient to use equivalent amounts of the reactants but there is no harm in a major excess of formaldehyde.

Examples of suitable aqueous-organic solutions are mixtures of water with methanol, ethanol, gylcol, methyl glycol, ethyl glycol, diethylene glycol, dioxane, pyridine, dimethylfonnamide or N-methyl-pyrrolidone.

Details of the production of the new compounds are given in the following Examples.

The new compounds of the formula (I) are valuable intermediates for the production of dyes.

EXAMPLE 1 calculated c 58.9 H 3.9 N |3.7 o 23.6

found 59.2 4.1 13.4 23.5

EXAMPLE 2 234 parts of N-butyl--nitroisoindol-l-one is dis solved in 400 parts by volume of methyl glycol at 100C. parts of 40 percent aqueous formaldehyde solution and 10 parts by volume of piperidine are added and the whole is stirred for four hours at 105C. The solution is then poured into 1,000 parts of water and allowed to stand overnight. By that time the reaction product has settled as a cake of crystals. The supernatant liquid is decanted off, and the cake of crystals is washed several times with water and then dried at 50C at subatomospheric pressure. 236 parts of N- butyl-3-methylene-o-nitroisoindol-1-one is obtained. A sample recrystallized from ethanol melts at 1 12C.

EXAMPLE 3 250 parts of N-(y-methoxypropyl)-6-nitroisoindoll-one, 250 parts by volume of methyl glycol, parts by volume of 40 percent aqueous formaldehyde solution and 25 parts by volume of piperidine are stirred for nitroisoindol-l-one is obtained having a melting point of l3lto 132C.

nitroisoindol-l-one is obtained having a melting point [5 of 220C (with decomposition).

EXAMPLE 5 A mixture of 500 parts by volume of dioxane, l50 parts by volume of 40 percent aqueous formaldehyde solution, 290 parts of N-( B-ethylhexyl )-6- nitrolisoindol-l-one and parts by volume of piperidine is boiled under reflux for six hours. The reaction mixture is then poured into 1,000 parts of water and the deposited oil is taken up in chloroform. The chloroform solution is made neutral with acetic acid, washed with water and dried over potassium carbonate. After filtering the product and distilling off the solvent, 291 parts of N-(B-ethylhexyl)-3-methylene-'nitroisoindoll-one remains as a highly viscous oil. The compound cannot be distilled without decomposition.

EXAMPLE 6 260 parts of N-cyclohexyl-fi-nitroisoindohl-one is dissolved in 400 parts by volume of pyridine with heating. 200 parts by volume of percent formaldehyde solution and 10 parts by volume of piperidine are added and the whole is boiled for two hours. The solution is then poured onto ice and excess hydrochloric acid and the precipitated product is suction filtered, washed with water and dried. 268 parts of N- cyclohexyl-3-methylene-6-nitroisoindol-l-one is obtained. A sample recrystallized from amyl alcohol melts at 195C.

EXAMPLE 7 382 parts of the compounds 7 H C a HzC is introduced into a mixture of 500 parts by volume of pyridine and 30 parts by volume of 40 percent aqueous formaldehyde solution and boiled. The compound passes into solution after a short time and after about one hour the reaction product begins to crystallize out. The whole is boiled for a total of 6 hours, diluted with 500 parts by volume of water, suction filtered, washed with 1 percent acetic acid and dried. 32.3 parts of the compound of the formula:

10 is obtained having a melting point of 292C (with decomposition).

The compounds identified in the following Table by n and R may be obtained by methods analogous to ho describ ab v Example l claim: 1. A 3-methylene-6-nitroN-substituted isoindolone- (1) of the formula:

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3 3,818,037

DATED 1 June 18, 1974 |NV ENTOR(S) Ernst Schefczik It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 1, in the heading, insert-[30] Foreign Application Priority Data, November 13, 1970, Germany,

P 20 55 8l6.l-;

Column 3, line'22, delete "nitrolisoindol" and substitutenitroisoindol-;

Column 4, line 41, delete"nitroN" and substitute -nitro-N;

Column 4, line 56, delete "2 and" and substitute 2; and. 7

g and Sealed this [SEMI twenty-fifth Of November 1975 Arrest:

RUTH C. MASON C. MAR JIIUSIIHX Officer SHALL DANN 

